Esters of hydroxyalkyl aromatic sulfonamides



iatented Feb. 7, 195$ ESTERS F HYDROXYALKYL AROMATIC SULFONAMIDES David Aelony, Minneapolis, Minn, assignor to General Mills, Inc, a corporation of Delaware No Drawing. Application May 15, 1947, Serial No. 748,335

The present invention relates to esters of hydroxyalkyl aromatic sulfonamides. Members of this group of compounds are useful as plasticizers, waxes, and the like. The present application is a continuation-in-part of my copending application, Serial No. 643,748, filed January 26, 1946, entitled Esters of hydroxyallryd aromatic sulfonamides.

In general, the compounds contemplated by the present invention may be represented by the following structural formula:

RSOaN in which R is an aromatic radical such as phenyl, toluyl, xylyl, naphthyl, thienyl, or derivatives thereof; R may be hydrogen, an aliphatic hydrocarbon radical such as methyl, ethyl, propyl, and the like, aryl such as phenyl, toluyl, xylyl, and the like; R is alkylene such as methylene, ethylene, propylene, and the like; and R is an aliphatic hydrocarbon radical such as methyl, ethyl, propyl, heptyl, nonyl, pentadecyl, heptadecyl, and the like. The letter it may represent the integers one or two.

The lower esters, such as the acetates, butyrates, crotonates, and the like, are liquids which have been found to be useful as plasticizers for polyvinyl resins, particularly polyvinyl chloride resins. Polyvinyl resins are generally too hard and rigid to be used for many purposes without a plasticizer. It is usually necessary to add a plasticizer to make the resin soft and pliable and capable of being milled into strong pliable sheets or films. It is also necessary that the plasticized resin composition have excellent heat stability, supp-leness and elasticity. In order for a material to act as a plasticizer, it is necessary that it be compatible with the resin and not exude or sweat out to leave the resin unplasticized.

There have been found very few plasticizers which are really satisfactory for this purpose. The esters of dibasic acids, such as phthalic and sebacic acid, have been most widely used for plasticizing such resins. However, unless the esters are derived from alcohols of fairly high molecular weight, such as octyl alcohol, the plasticizers are of too low a molecular weight, and therefore too volatile for many uses. The plasticizers which are sufficiently non-volatile and which also have the ability to give flexibility at low temperature and some measure of stability against heat discoloration, are quite limited in number. Furthermore, the heat stability of such compounds is generally not particularly satisfactory.

The lower esters herein described are, in general, highly satisfactory as plasticizers for resins in general, and particularly for the polyvinyl resins. They exhibit good compatibility, elonsa- 7 Claims. (Cl. 260- 101) tion, thermal stability, color, and hand or feel. At the same time, they render the plastics flexible at low temperature. Moreover, the plasticizers are of a high boiling point and consequently are not lost through volatilization during use.

The higher fatty acid esters of these sulfonamides in general are useful as waxes. Compounds which are useful as waxes in general should be relatively inert chemically, should be light color, non-crystalline, and melt at an elevated temperature, for example at -100 C. They should also form gels in solvents, emulsify to form liquid polishes, and produce a good hard shiny surface which will not mar easily. Waxes heretofore available have not been completely satisfactory in various respects. Either they are too high in cost or lack the necessary properties of good waxes. The wax compounds of the present invention constitute improvements on the compounds which have been available heretofore. The various compounds of the present inven-' tion may be prepared by reacting an aromatic sulfonyl halide with an alkanolamine to form the hydroxyalkyl aromatic sulfonamide which may then be treated with an acylating agent to form the ester. It will be apparent that the alkanolamine may be a monoor dialkanolamine, and in the event that a dialkanolamine is employed, it will be apparent that this may subsequently be partially or completely esterified. The reaction conditions which are suitable are illustrated by the following examples.

EXAMPLE 1 N,N di-beta-hydroxyethyl benzene suljonamz'de distearate 202 g. benzene sulfonchloride were slowly added to an agitated cold solution of g. sodium carbonate and g. diethanolamine in 400 cc. of water. The resultant mixture gradually came to a boil and was refluxed for 1 hour, whereupon it was allowed to stand and was separated into two layers. The lower layer was extracted with chloroform, Washed with a little cold water, dried over NazsOafiltered and evaporated in vacuo on a steam bath. 238 g. ofv a heavy liquid N 1.545! were obtained. The percent N found was 5.60 (theory for N,N-di-beta-hydroxyethyl benzene sulfonamide, 5.71) hydroxyl number ifOllIld. was 420.7 (theory 458) percent free amino group, less than 0.4%.

g. of a commercial stearic acid (Neo fat 1-65), 73.5 g. N,N-di-beta-hydroxyethyl benzene sulfonamide, 300 cc. xylene and 5 g. p-toluene sulfonic acid hydrate were agitated and refluxed over a Starck and Dean tube. In five hours, 11 cc. of water (theory for the distearate, 12.5 cc.) were collected in the trap. The product was dried in vacuo on a steam bath yielding 220 g. of a solid M. 1?. 75-6 0., percent N found 1.74 (theory 1.81), acidNo. 13.5. Wax gels containing 25% solids and 75% solvent were made using turpentine and also with mineral spirits. These wax gels imparted beautiful polishes to shoes, furniture, and cars.

EXANIPLE 2 N-beta-hydromyethyl benzene suljonamz'de stearate 40 g. monoethanolamine and 53 g. sodium carbonate were dissolved in 300 cc. H20, and 113 g. of benzene sulfonchloride were then added slowly. The mixture was heated on a steam bath and agitated occasionally for four hours at which time two layers were formed on standing. The lower layer was extracted with chloroform and the chloroform solution was dried over sodium sulfate, filtered, andevaporated in vacuo yielding 123 g. (93% theory) of a viscous liquid which upon fractionation in vacuo yielded 106 g. liquid of pale straw color, N 1.5515, percent N found 6.97 (theory for ,N-beta-hydroxyethyl benzene sulfonamide, 6.96) hydroxyl number found 555.5

(theory 556) boiling point 172 C. at 40 microns pressure.

100 g. N-beta-hydroxyethyl benzene sulfonamide, 140 g. of a commercial stearic acid (Neo fat 1-65), 2.5 g. p-toluene sulfonic acid monohydrate and 400 cc. xylene were agitated and refluxed over a Starck and Dean tube. In 2 hours the reaction was complete, and nearly 9 cc. water was collected. Xylene was removed by distillation in vacuo. The residue was poured into dilute ammonium hydroxide solution; then acidified with I-ICl, filtered, Washed with water until neutral, then with a little alcohol and allowedto dry. It was recrystallized twice from alcohol yielding 71% of a material M. P. 79-79.5 0., percent N found 2.97 (theory for the stearate, 3.02) acid number 4.7. The product yielded a softish gel with 75% turpentine, but a very firm one with 75% mineral spirits. Excellent shines on shoes, furniture, and cars were obtained with each.

EXAMPLE 3 N-beta-hydrowyethyl p-toluene sulfonamide steiirate 250 g. monoethanolamine were dissolved in 1 liter of water. 381 g.,p-toluene sulfonchloride were added with agitation. The temperature went up to 65 C. The reaction mixture was brought up to a boil and was allowed to stand overnight. The lower layer was dissolved in chloroform, washed with a little cold water, dried over sodium sulfate, filtered and evaporated. It was distilled in vacuo yielding 357 g. material, boiling point 208 C. at 40 microns pressure. Two days after distillation it solidified.

.134 g. N-beta-hydroxyethyl p-toluene sulfonamide, 175 g. of a commercial stearic-acid (Neo fat 1-65) and 200 cc. xylene were agitated and refluxed under a Starch and Dean tube for 3 hours. The temperature was allowed to go up to 230 C. by gradually draining the distillate. 11.5 cc. water were collected (theory for the stearate, 11.2 cc.). The solvent was stripped. in vacuo. The product, a dark brown solid of buttery consistency was obtainedin a 295 g.-yield (theory 298 g), percent N found 2.89 (theory 2 .97). The product was extremely soluble in most ordinary organic solvents such as benzene, alcohol, carbon tetrachloride, etc., with the exception of aliphatic hydrocarbons.

EXALAPLE 4 N,N-di-beta-hyromyethyl p toluene sulfonamz'de distearate 210 g. diethanolamine were dissolved in 700 cc. water and the mixture was heated to 70 C. 190.5 g. p-toluene sulfonchloride were added at once. A violent reaction accompanied by boiling took place, and a homogeneous solution resulted. On cooling, a dark lower layer separated which solidified at 45 C. It was filtered and recrystallized from methanol yielding 156 g. white crystals M. P. 101.5103.5 C. and 42 g. white powder (from mother liquor) M. P. 9'7.5-100 C. The total yield was 76.5% theory.

129.5 g. N,N-di-beta-hydroxyethyl p-toluene sulfonaniide, 280.5 g. of a commercial stearic acid (Neo fat 1-65), 1 g. p-toluene sulfonic acid monohydrate and 250 cc. xylene were refluxed over a Starch and Dean tube for two hours. A total of 18 cc. of water was collected in the trap. The product was poured into 1.5 liters butanol, was allowed to stand overnight and filtered. After five days of air drying 353.5 g. of the product (92% yield) M. P. 68.5-69.5" C. were obtained. Percent N found 1.765 (theory for the stearate, 1.78), acid number 2.4. When melted and allowed to solidify, a beautiful hard shiny solid is formed (penetration in 30 see. with a 200 g. load, ASTM needle, was 3, while it was 1 for Carnauba No. 1). Fine 25% Wax gels were made using turpentine or mineral spirits as solvents. The gels possess excellent polishing properties.

EXANIPLE 5 N,N-di-beta-hydroxyethyl p-toluene sulfonamz'de diacetate EXAMPLE 6 N,N-di-beta-hydro.ryethyl p-toluene sulfonamide dibutyrate g. N,Ndi-beta-hydroxyethyl p-toluene sulfonamide, 70 g. n-butyric acid, 250 cc. xylene and 0.5 g. of p-toluene sulfonic acid hydrate were agitated and refluxed over a Starck and Dean tube for 4 hours. 14 cc. of water were collected (theoretical). Xylene was distilled off" and the residue was distilled in vacuo with slight decom position. 118 g. distilled at 238 C. at 0. 1 mm., N 1.5002; per cent N found 3.52 (theory 3.51).

EXAMPLE 7 -N,N-di-beta-hydromyethyl beta-naphthalene s'uljonamide distearatc 100 g. beta-naphthalene sulfonchloride, g. diethanolamine, and 300 cc. water were stirred two hours on a steam bath. The cooled product was filtered and recrystallized from methanol yielding 77 g., M. P. 92-4 0.; 9 g., M. P. 82-5 C. and 46 g. material of buttery consistency obtained by evaporation of mother liquor.

70.5 g. N,N-dl-beta-hydroxyethyl beta-naphthalene sulfonamide, 134 g. of a commercial stearic acid (Neo fat 1-65), 1 g. toluene sulfonic acid monohydrateand 300 cc. of xylene were agitated and refluxed over a Starck and Dean tube for two hours. 8.5 cc. water were collected. The product was recrystallized from butanol and then from methanol yielding 153 g. wax, M. P. 78.5-80" C. Wax gels prepared from the wax had good polishing properties.

EXAMPLE 8 N-ethyl, N-hydrocwethyl benzene sulfonamide acetate N-ethyl, N-hydroxyethyl benzene sulfonamide acetate was prepared by refluxing 100 g. N-ethyl, N-hydroxyethyl benzene sulfonamide with 95 cc. acetic anhydride for 3 /2 hours. It was fractionated, yielding 113 g. white liquid, boiling point at 150 microns of 184 C., N 1.5133, and 5 g. residue. The yield was nearly theoretical. Sap. Eq. 277.3; 277.8 (theory 271); percent N 5.10 (theory 5.16).

EXAMPLE 9 N-ethyl, N-hydrozcyethyl benzene sulfonamtde butyrate N-ethyl, N-hydroxyethyl benzene suli'onamide butyrate was prepared by refluxing 76 g. N-ethyl, N-hydroxyethyl benzene sulfonamide and 84 cc. butyric anhydride for 4 hours. It was fractionated in vacuo yielding:

Fraction #1B. P. at 100 microns of 177 C., 5.5 g., N 1.4987.

Fraction #2B. P. at 100 microns of 180 C.,

Fraction #2 was 83% theory. Sap. Eq. 312 (theory 299), percent N 4.68 (theory 4.68).

EXAMPLE 10 Ill-ethyl, N-hydrozcyethyl benzene snlfonamtde caprylate N-ethyl, N-hydroxyethyl benzene sulfonamide caprylate was prepared by refluxing and agitating under a Starck and Dean tube 72 g. caprylic acid (Neo fat #7), 114.5 g. N-ethyl, N-hydroxyethyl benzene sulfonamide, 5 g. p-toluene sulfonic acid hydrate and 300 cc. xylene for 5 hours. The product was washed with NazCOs, H2O, dried over NaaSO-r, filtered, evaporated and distilled. First fraction with boiling point at 20 microns below 165 C. was discarded. The second fraction had the following properties: boiling point at 40 microns of 177-182 C., N 1.4987, saponification equivalent 428.7, 428.5 (theory 355).

EXAMPLE 11 N ethyl, N-hydrowyethyl benzene snljonamide caprate 6 tion, g., boiling point at'200 microns of 225 6., N 1.4964 (84% theory), acid No. 0.33, Sap. Eq. 393.3, 393.6 (theory 383),percent N 3.67 (theory 3.65), residue 6 g.

', EXAMPLE 12 N-ethyl, N-hydroscyethyl benzene sulfonamtde lc'urate (1) B. P. at 12-60 microns of 112455 0., 59 g.,

semi-solid at room temperature. (2) B. P. at 25 microns of l40160 (3., 1'7 g. (3) B. P. at 40 microns of 140-170 C., 18 g. (4) B. P. at 30 microns of 215-220 C., 41 g., N 1.4918, acid NO. 3.4:, Sap. Eq. 416.7, 415.8

(theory 411).

EXAMPLE 13 N-eth' Z, N-hydroxyethyl benzene snljonamide myrz'state N-ethyl, N-hydroxyethyl benzene sulfonamide myristate was prepared in 87.9% yield by refluxing 118 g. myristic acid (Neo fat 13), 114.5 g. 'N-ethyl, N-hydroxyethyl benzene sulfonamide, 5 g. p-toluene sulfonic acid hydrate and 300 cc. xylene for 2%; hours. 95.5% theoretical H2O was collected. It was washed with P120, NHiOH (emulsion). The emulsion was broken with alcohol. The xylene solution was dried, filtered, evaporated, and distilled. Fraction #1, boiling point at 40 microns of 225 C., 17 g., ND24 1.4935, Sap. Eq. 466, percent N 3.00; fraction #2, 192 g., boiling point at 50 microns of 240 0., H13 1.4915, Sap. Eq. 443 (theory 439), percent N 3.14 (theory 3.18).

EXAMPLE 14 N-ethyl, N-hydromyethyl benzene snljfonamtde stearate N-ethyl, N-hydroxyethyl benzene sulfonamide stearate was prepared in a 94% yield after 3 hours of refluxing g. N-ethyl, N-hydroxyethyl benzene sulfonamide, 233 g. commercial stearic acid (Neo fat 1-65), 5 g. toluene sulfonic acid hydrate, and 700 cc. xylene. The product is a brown, buttery solid which can be distilled (boiling point at 40 microns of 242 C.). Acid number of undistilled solid 4.6, 4.1; percent N 2.84.

EXAMPLE 15 N-butyl, N-hydromyethyl benzene sulfonamide acetate V N, n-butyl, N, beta-hydroxyethyl benzene sulfonamide acetate was prepared by refluxin for two hours 46 g. recovered N-butyl, N-hydroxyethyl benzene sulfonamide with 100 cc. acetic anhydride. Acetic acid and anhydride were removed by distillation in vacuo (water pump) and the residue-was distilled in high vacuo yielding 42 g. of a straw-colored liquid, boiling point at 8-microns of. 153-4 C., No 1.5075, percent N found 4.58. (theory 4.68). I

7 EXAMPLEJS N-butyl', N-hydromyethyl benzene suljonamide butyr'ate N-buiyl N-hydrozcyethyl benzene sulfonamide caprylate N-butyl, N-hydroxyethyl benzene sulfonamide caprylate was prepared byrefluxing, and agitating 66.2 g. caprylic acid, 118 g. N-butyl, N-hydroxyethyl benzene sulfonamide, 5 g p-toluene sulfonic acid hydrate and 3 cc. xylene for 5 hours. The product was washed with g. NazCOa, H2O, dried over NazSOa, filtered, evaporated and distilled in vacud. yielding a product with bOillIlg point at 10 microns of 184-492 C., ND 14945, percentN 3.73, 3.71 (theory 3.65), saponification equivalent 394, 39.6 (theory 383).

EXAIMPLE 18 N butyl,

caprate N-butyl, N-hydroxyethyl benzene sulfonamide caprate was prepared in a 94% yield (based on distillate alone) by refluxing for 3 hours. 129. g. N-butyl, N-hydroxyethyl benzene sulfonam'ide, 86 g. A mol) capric acid (Neo fat15),f5 g. ptoluene sulfonic acid hydrate and300. cc. xylene. The reaction was almost complete in, 1, hour (96.6%). The product was washed with H2O, dried over Nazsoi, filtered and distilled. Fraction No. 1, boiling point at microns of 220 C., 31 g., N19 1.4925; fraction No. 2, boiling point at 30 microns of 209-211 C., 162 g., N13 1.4927, residue 5 g.

N ,N-dihydrexyethyl p-to'luene suljonamz'de diacetate saponiflcation equivalent N-hydroxyethyl' benzene sulfonamide N,N-dihydroxyethyl p-toluene sulfonamide 'diacetate was preparedin an 88% yiel'd'by refluxing g. tlN-dihydroxyethyl p-toluene sulfonamide and 55 g. acetic anhydride for 3 hours. cc. water was added, refluxed for affew minutes, made alkaline with NazCOsv and extracted} with ether. The ether extract was washed, dried, filtered, and evaporatedyielding 64 g. of a liquid, Nn 1.5103, saponification equivalent was 177.7 (theory 176.5), percent 174.025 (theory-3.97).

EXAMPLE 20 N,l l-diiryd. oryethyl p-toluene sulfonamide d1.- crotonate N,N-dihydroxyetnyl p-toluene sulfonamide. dicrotonate was prepared in an 82.% yield by refluxing 259 grams N,N,-dihydroxyethyl p-toluene sulfonamide, 250 grams commercial. crotonic acid, 10 grams p-toluene-sulfonic acid and 500 cc. xylene for 7.5.hours over a Starck and Dean tube.

After washing, drying, and evaporating,

v in 10000. of water.

the product was distilled in vacuo yielding a tea-colored liquid ND 1.5232, percent N 3.73, 3.63 (theory 354), acid number 2.02, Sap. Eq. 208:4, 207.8 (theory 197.5), specific gravity 1.1966.

INN-dihydromyethyl p-dichlorbeneenesulfonamide diacetate 142 g. of p-'chlorbenzenesulfonchloride was added over a. 20 minute'peri'od to a stirred boiling solution of 76 g. of diethanolamine, 72 g. of sodium carbonate, and 1 liter of water. The mixture was agitated and refluxed for 6 hours, after which it was neutralized with 37 g. sulfuric acid dissolved Theresultant mixture was cooled and filtered. The precipitate was extracted with methanol and the hot methanol solution was cooled and filtered. The precipitate Weighed 13. g. .The mother liquor was evaporated yielding g..of awhite solid.

70 g. N,N-dihydroxyethyl chlorbenzene sulfonamide was converted in 76% yield to the diacetate by refluxing it with 100 cc. acetic anhydride for three hours. It. was filtered hot and fractionated yielding 69 g. low melting solid, boilingpoint at. 12; microns of -193 0., saponification equivalent 194.6 (theory 182.8), per cent N 3.92 (theory 3.85).

EXAIVIPLE' 22 MN-dihydromytityl p-dz'chlorbenzenesulfonamide dicaprylate 37 g. N,N-dihydroxyethyl p-dichlorbenzenesulfonami'de, 34 g. caprylic acid (Neo fat 7), 2 g. p-toluene sulfonic acid hydrate, and 250 cc. xylene were agitated and refluxed over a Starck and Dean tube. Theoretical water distilled in 3 hours. The product 'was allowed tocool. It was washed with NazCOa, H2O, dried over NazSO4.

evaporated, and distilled in vacuo. Only a few cc. distilled over below 205 C. at 20 microns. At 227-232 C. at 10111101011848 g. of liquid distilled over. This liquid hadaND 1.5035, Sap. Eq. 278.6 (theory 283) EXAMPLE 23 N,N-dihydroa2yethyl thzophene sulfmzamide diacetate N,N-dihydroxyethy-l thiophene sulfonamide diacetate was prepared'by refluxing 100 g. N,N-dihydroxyethyl thiophenesulionamide and 200 cc. acetic anhydride for 4 hours. The product was evaporated and distilled in vacuo:

Fraction #1-B. P. at

50 microns, of 188 C. 12 g., ND 1.5425 Fraction #2-B. 'P. at

50-70 microns of 192- 205- C', 88 g., 5713 15153 Residue 10g. Sap. Eq. ((1 h e-ory 167.5) Per cent N (theory 4.18) F-r a 0 ti o n #1-2393;

238.9 3.82; 3.77; 3.82- F-rac t io n #2-176.9-;

EXAMPLE 24 N=hydrozcyethyl, N-llhcnyl benzene sulfonamide acetate N-benzenesulfonyl, N phenyl ethanolamine acetate was prepared in a 93% yield by refluxing 70 g. N'-pheny1, N-benzenesulfonyl ethanolamine and 80 cc. acetic anhydride for hours. It was allowed to stand overnight. The acid and the anhydride were distilled off first. The residue was then distilled at 185188 C. at 30 microns. It weighed 75 g., N1) 1.5570, per cent N 4.32, 4.30 (theory 4.39).

The esters of N-alkyl, N-hydroxyethyl benzene sulfonamides prove particularly desirable as plasticizers for polyvinyl resins. This is demonstrated by the table given below which shows the properties of polyvinyl resins plasticized with these particular compounds. The plasticized compositions were prepared as follows: 63.5 g. Vinylite VYNW (Carbide 8: Carbon), 0.5 g. stearic acid, 1 g. basic lead carbonate, 35 g. plasticizer, are mixed and milled on a heated roller mill at 140-150" C. The results of these tests are indicated as follows:

Esters of N-ethyl, N-hydrowyethyl benzene Esters of N-butyl, N-hydrowyethyl benzene suljonamide Heat Sweating v Mm. Ester Elongation stability in 24 hrs. at 0. Flex Percent Hours 0.

10 While various modifications of the above invention have been described, it is to be understood that this invention is not limited thereto, but may be varied within the scope of the following claims.

I claim as my invention: 1. An ester of a hydoxyalkyl aromatic sulfonamide having the following structural formula:

nsom

' of the ester being a higher fatty acid group.

5. An ester of N-ethyl, N-hydroxyethyl benzene sulfonamide, said ester containing a fatty acid group containing at least 8 carbon atoms.

6. An ester of N-butyl, N-hydroxyethyl benzene sulfonamide, said ester containing a fatty acid group containing at least 8 carbon atoms.

7. N-ethyl, N-hydroxyethyl benzene sulfonamide monolaurate.

DAVID AELONY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,036,932 Felix et a1. Apr. 7, 1936 40 2,097,414 Kharasch et a1. Oct. 26, 1937 2.187.823 Ulrich et a1 Jan. 23, 1940 

1. AN ESTER OF A HYDOXYALKYL AROMATIC SULFONAMIDE HAVING THE FOLLOWING STRUCTURAL FORMULA: 